Derivatives of a 1-phenyltriazole

ABSTRACT

Compounds of formula (I) 
                         
wherein
         X is chloro or bromo;   Y is chloro or trifluoromethyl; and   A and B are hydrogen or methyl with the proviso that one of A or B must be methyl; or the enantiomers or salts thereof,
 
use of compounds of formula I for combating insects or acarids and for treating, controlling, preventing or protecting animals against infestation or infection by parasites, and compositions comprising compounds of formula I.

This application is a National Stage application of InternationalApplication No. PCT/EP2006/062719, filed May 30, 2006, which claims thebenefit of U.S. Provisional Application No. 60/687,027, filed Jun. 3,2005, wherein the entire contents of both are hereby incorporated hereinby reference.

The present invention relates to compounds of formula (I)

wherein

X is chloro or bromo;

Y is chloro or trifluoromethyl; and

A and B are hydrogen or methyl with the proviso that one of A or B mustbe methyl;

or the enantiomers or salts thereof for combating insects or acarids.

The present invention also provides methods for the control of insectsand acarids by contacting the insect or acarid or their food supply,habitat or breeding grounds with a pesticidally effective amount ofcompounds or compositions of formula I.

Moreover, the present invention also relates to a method of protectinggrowing plants from attack or infestation by insects or acarids byapplying to the foliage of the plants, or to the soil or water in whichthey are growing, with a pesticidally effective amount of compositionsor compounds of formula I.

This invention also provides a method for treating, controlling,preventing or protecting animals against infestation or infection byparasites which comprises orally, topically or parenterallyadministering or applying to the animals a parasiticidally effectiveamount of compositions or compounds of formula I.

The invention also provides a process for the preparation of acomposition for treating, controlling, preventing or protecting awarm-blooded animal or a fish against infestation or infection byinsects and acarids which comprises a pesticidally effective amount of acompound having the formula I.

In spite of the commercial insecticides and acaricides available today,damage to crops, livestock, companion animals and humans still occurs.Accordingly, there is on-going research to create new and more effectiveinsecticides and acaricides. It was therefore an object of the presentinvention to provide new insecticidal and acaricidal compounds, newcompositions and new methods for the control of insects or acarids.

We have found that these objects are achieved by the compounds andcompositions of formula I.

1-Phenyltriazoles have been described inter alia in EP-A 957 094 and inEP-A 285 893. The insecticidal and acaricidal properties of thesecompounds however are not totally satisfying.

It was therefore an object of the present invention to provide new1-phenyltriazoles having enhanced properties for combating insects andacarids.

Accordingly, 1-phenyl-1,2,4-triazoles of formula I were found whichexhibit a methyl group at the 1-position of the cyclopropyl ring and/orat the 5-position of the triazole ring.

EP-A 957 094 discloses 1-(2-halogenaryl)azoles wherein the aryl groupmay be substituted phenyl and the azole may be 1,2,4-triazole, which maycarry an optionally substituted cyclopropyl ring. No mention is madehowever of the favorable effect of fixing a methyl group at thecyclopropyl ring or at the triazole ring.

EP-A 285 893 describes 1-phenyl-(1,2,4-triazoles) wherein the triazolein the 3-position among a broad group of substituents may carry amethyl-substituted cyclopropyl group but preferably an alkyl orhaloalkyl group and in the 5-position is optionally substituted,preferably by an amino derived group. EP-A 285 893 does not disclose the1-phenyl-triazoles of the present invention nor does it suggest thefavorable effect of fixing a methyl group at the cyclopropyl ring and/orat the triazole ring.

Depending on the substitution pattern, the compounds of formula I cancontain a chiral center, in which case they are present as enantiomermixtures. Subject-matter of this invention are not only compositionscontaining these mixtures but also those containing the pureenantiomers.

Compounds of formula I may be synthesized by reacting compounds offormula II

wherein R is methyl, ethyl or trimethylsilyl, with an oxidating agent.

Suitable oxidating agents are, for example, lead (IV)-oxide (PbO₂),hypochlorites (e.g. NaOCl) and dichlorodicyanobenzoquinone (DDQ).

Particular preference is given to dichlorodicyanobenzoquinone (DDQ).

The reaction is usually carried out at temperatures of from −20° C. to50° C., preferably from −5° C. to 25° C. (room temperature), in an inertorganic solvent in the presence of a base.

Suitable solvents are aromatic hydrocarbons such as toluene, o-, m- andp-xylene, aliphatic hydrocarbons such as pentane, hexane, cyclohexaneand petroleum ether, halogenated hydrocarbons, such as methylenechloride, chloroform and chlorobenzene, ethers, such as diethyl ether,diisopropyl ether, tert.-butyl methyl ether, dioxane, tetrahydrofurane,diglyme or anisol, nitriles such as acetonitrile and propionitrile, andalso dimethyl sulfoxide, dimethyl formamide and dimethyl acetamide.Particular preference is given to aromatic hydrocarbons. It is alsopossible to use mixtures of the solvents mentioned.

Suitable bases are organic bases, such as tertiary amines, such astrimethyl amine, triethyl amine, diisopropyl ethyl amine,N-methyl-piperidine, and pyridine. Substituted pyridines are for examplecollidine, lutidine and 4-dimethyl amino pyridine as well as bicyclicamines such as quinoline or isoquinoline. Further suitable bases areinorganic compounds such as alkali metal hydroxides and earth alkalimetal hydroxides such as lithium hydroxide, sodium hydroxide, potassiumhydroxide, and calcium hydroxide, alkali metal oxides and earth alkalimetal oxides such as lithium oxide, sodium oxide, potassium oxide,calcium oxide, and magnesium oxide, alkali metal carbonates and earthalkali metal carbonates such as lithium carbonate, potassium carbonate,and calcium carbonate, alkali metal hydrogen carbonates such as sodiumhydrogen carbonate, alkali metal alcoholates and earth alkali metalalcoholates such as sodium methanolate, sodium ethanolate, potassiumethanolate, potassium tert.-butanolate and dimethoxy magnesium.Particular preference is given to pyridine and substituted pyridines. Itis also possible to use mixtures of the bases mentioned.

In general, the base is employed in equimolar amounts, in excess, or asa solvent.

Compounds of formula ll are obtainable according to procedures describedin EP-A 604 798.

With respect to the intended use of the compounds of formula I,particular preference is given to the following meanings of thesubstituents, in each case on their own or in combination:

Preference is given to compounds of formula I wherein X is chloro.

Moreover, preference is given to compounds of formula I wherein Y istrifluoromethyl.

Preference is also given to compounds of formula I wherein A is methyl.

Moreover, preference is given to compounds of formula I wherein B ismethyl.

Particular preference is given to compounds of formula I wherein A ismethyl and X is chloro.

Particular preference is also given to compounds of formula I wherein Bis methyl and X is chloro.

Particular preference is also given to compounds of formula I wherein Aand B are each methyl.

Particularly preferred are the following compounds:

1)1-(2,6-dichloro-4-trifluoromethylphenyl)-3-(1-methyl-2,2-dichlorocyclopropyl)-5-methyl-1,2,4-triazole;and

2)1-(2,6-dichloro-4-trifluoromethylphenyl)-3-(2,2-dichlorocyclopropyl)-5-methyl-1,2,4-triazole.

The most preferred compound according to the present invention is1-(2,6-dichloro-4-trifluoromethylphenyl)-3-(1-methyl-2,2-dichlorocyclopropyl)-5-methyl-1,2,4-triazole.

The compounds of the formula I are suitable for efficiently controllinginsects and acarids in crop protection and in combating non-crop pests.

The compounds of the formula I are especially suitable for efficientlycombating the following pests:

insects from the order of the lepidopterans (Lepidoptera), for exampleAgrotis ypsilon, Agrotis segetum, Alabama argillacea, Anficarsiagemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius,Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneurafumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydiapomonella, Dendrolimus pini, Diaphania nitidalls, Dlatraea grandiosella,Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella,Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholithafunebrana, Grapholitha molesta, Hellothis armigera, Hellothis virescens,Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea,Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria,Laphygma exigua, Leucoptera coffeella, Leucoptera scitella,Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis,Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosomaneustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalls,Panolls flammea, Pectinophora gossypiella, Peridroma saucia, Phalerabucephala, Phthorimaea operculella, Phyllocnistis citrella, Pierisbrassicae, Plathypena scabra, Plutella xylostella, Pseudoplusiaincludens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotrogacerealella, Sparganothis pilleriana, Spodoptera fruglperda, Spodopteralittoralls, Spodoptera litura, Thaumatopoea pityocampa, Tortrixviridana, Trichoplusia ni and Zeiraphera canadensis,

beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus,Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar,Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athoushaemorrhoidals, Atomaria linearis, Blastophagus piniperda, Blitophagaundata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscusbetulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata,Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis,Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabroticalongicornis, Diabrotica semipunctata, Diabrotica 12-punctata Diabroticaspeciosa, Diabrotica virgifera, Epilachna varivestis, Epitrixhiirtpennis, Eutinobothrus brasiilensis, Hylobius abietis, Hyperabrunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lemamelanopus, Leptinotarsa decemlineata, Limonius californicus,Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus,Melolontha hippocastani, Melolontha melolontha, Oulema oryzae,Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae,Phyllobius pyri, Phyllotreta chrysocephala, Phyllophaga sp.,Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata,Popillia japonica, Sitona lineatus and Sitophilus granaria,

flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedesvexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians,Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anophelesleucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphoravicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax,Chrysomya macellaria, Chrysops discails, Chrysops silacea, Chrysopsallanticus, Cochliomyla hominivorax, Contarinia sorghicola Cordylobiaanthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus,Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culisetamelanura, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Deliaantique, Delia coarctata, Delia platura, Della radicum, Dermatobiahominis, Fannia canicularis, Geomyza Tripunctata, Gasterophilusintestinalis, Glossina morsiftans, Glossina palpalis, Glossina fuscipes,Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris,Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconopstorrens, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Luciliacuprina, Lucilla sericata, Lycoria pectoralis, Mansonia titillanus,Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis,Opomyza florum, Oscinella frit, Pegomya hysocyami, Phorbia antiqua,Phorbia brassicae, Phorbia coarctata, Phlebotomus argentipes, Psorophoracolumbiae, Psila rosae, Psorophora discolor, Prosimullum mixtum,Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga haemorrhoidalis,Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus,Tabanus atratus, Tabanus lineola, and Tabanus similis, Tipula oleracea,and Tipulapaludosa

thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp,Frankliniella fusca, Frankllniella occidentalls, Frankllniella tritici,Scirtothrlps citri, Thrips olyzae, Thrips palmi and Thrips tabaci,

termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes,Heterotermes aureus, Reticulltermes flavipes, Retfculltermes virginicus,Reticulltermes lucifugus, Termes natalensis, and Coptotermes formosanus,

cockroaches (Blattaria—Blattodea), e.g. Blattella germanica, Blattellaasahinae, Periplaneta americana, Periplaneta japonica, Periplanetabrunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blattaorientalis,

true bugs (Hemiptera), e.g. Acrosternum hilare, Blissus leucopterus,Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius,Eurygaster integriceps, Euschistus impictivenfris, Leptoglossusphyllopus, Lygus llneolaris, Lygus pratensis, Nezara viriduia, Piesmaquadrata, Solubea insularis, Thyanta perditor, Acyrthosiphon onobrychis,Adelges laricis, Aphidula nasturti; Aphis fabae, Aphis forbesi, Aphispomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphisspiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacofthum solani,Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi,Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae,Capiftophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii,Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphisradicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphispyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae,Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megouraviciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzus persicae,Myzus ascalonicus, Myzus cerasi, Myzus varians, Nasonovia ribis-nigri,Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida,Phorodon humuli, Psylla mall, Psylla piri, Rhopalomyzus ascalonicus,Rhopalosiphum maidis, Rhopalosiphum padi, Rhopalosiphum inserfum,Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneuralanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxopteraaurantiiand, Viteus vitifolli, Cimex lectularius, Cimex hemipterus,Reduvius senilis, Triatoma spp., and Arilus critatus.

ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Attacephalotes, Atta capiguara, Atta cephalotes, Afta laevigata, Attarobusta, Atta sexdens, Atta texana, Crematogaster spp., Hoplocampaminuta, Hoplocampa testudinea, Monomorium pharaonls, Solenopsisgeminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni,Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole megacephala,Dasymutilla occidentalis, Bombus spp. Vespula squamosa, Paravespulavulgaris, Paravespula pennsylvanica, Paravespula germanica,Dolichovespula maculata, Vespa crabro, Polistes rubiginosa, Camponotusfloridanus, and Linepithema humile,

crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica,Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus,Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes,Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americans,Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus,Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis,Kraussaria angulifera, Calliptamus itallcus, Chortoicetes terminifera,and Locustana pardalina,

Arachnoidea, such as arachnids (Acarina), e.g. of the familiesArgasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum,Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilusannulatus, Boophilus decoloratus, Boophilus microplus, Dermacentorsilvarum, Dermacentor andersoni, Dermacentor variabllis, Hyalommatruncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodesholocyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi,Ornithodorus turicata, Ornithonyssus bacoti, Otobius megnini,Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus sanguineus,Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei,and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrataoleivora and Eriophyes sheldoni, Tarsonemidae spp. such as Phytonemuspallidus and Polyphagotarsonemus latus; Tenuipalpidae spp. such asBrevipalpus phoenicis; Tetranychidae spp. such as Tetranychuscinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychustelarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, andOligonychus pratensis; Araneida, e.g. Lafrodectus mactans, andLoxosceles reclusa,

fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis,Xenopsylla cheopis, Pulex irriftans, Tunga penefrans, and Nosopsyllusfasciatus,

silverfish, firebrat (Thysanura), e.g. Lepisma saccharins and Thermobiadomestics,

centipedes (Chilopoda), e.g. Scutigera coleoptrata,

millipedes (Diplopoda), e.g. Narceus spp.,

Earwigs (Dermaptera), e.g. forifcula auricularia,

lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanuscorporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis,Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthusstramineus and Solenopotes capillatus.

Moreover, the compounds of formula I and compositions containing themare especially useful for the control of Isoptera, Diptera, Blattaria(Blattodea), Hymenoptera, Siphonaptera, and Acarina.

For use according to the present invention, the compounds I can beconverted into the customary formulations, e.g. solutions, emulsions,suspensions, dusts, powders, pastes and granules. The use form dependson the particular purpose; it is intended to ensure in each case a fineand uniform distribution of the compound according to the invention.

The formulations are prepared in a known manner, e.g. by extending theactive ingredient with solvents and/or carriers, if desired usingemulsifiers and dispersants. Solvents/auxiliaries, which are suitable,are essentially:

-   -   water, aromatic solvents (for example Solvesso products,        xylene), paraffins (for example mineral fractions), alcohols        (for example methanol, butanol, pentanol, benzyl alcohol),        ketones (for example cyclohexanone, gamma-butyrolactone),        pyrrolidones (NMP, NOP), acetates (glycol diacetate), glycols,        fatty acid dimethylamides, fatty acids and fatty acid esters. In        principle, solvent mixtures may also be used.    -   carriers such as ground natural minerals (e.g. kaolins, clays,        talc, chalk) and ground synthetic minerals (e.g. highly disperse        silica, silicates); emulsifiers such as nonionic and anionic        emulsifiers (e.g. polyoxyethylene fatty alcohol ethers,        alkylsulfonates and arylsulfonates) and dispersants such as        lignin-sulfite waste liquors and methylcellulose.

Suitable surfactants are alkali metal, alkaline earth metal and ammoniumsalts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonicacid, dibutyinaphthalenesulfonic acid, alkylarylsulfonates, alkylsulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids andsulfated fatty alcohol glycol ethers, furthermore condensates ofsulfonated naphthalene and naphthalene derivatives with formaldehyde,condensates of naphthalene or of naphthalenesulfonic acid with phenol®octylphenol, nonylphenol, alkylphenyl polyglycol ethers, tributylphenylpolyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyetheralcohols, alcohol and fatty alcohol/ethylene oxide condensates,ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylatedpolyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitolesters, lignin-sulfite waste liquors and methylcellulose and ethyleneoxide/propylene oxide block copolymers.

Substances which are suitable for the preparation of directly sprayablesolutions, emulsions, pastes or oil dispersions are mineral oilfractions of medium to high boiling point, such as kerosene or dieseloil, furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, for example toluene,xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or theirderivatives, methanol, ethanol, propanol, butanol, cyclohexanol,cyclohexanone, isophorone, strongly polar solvents, for example dimethylsulfoxide, N-methylpyrrolidone and water.

Powders, materials for spreading and dusts can be prepared by mixing orconcomitantly grinding the active substances with a solid carrier.

Granules, for example coated granules, impregnated granules andhomogeneous granules, can be prepared by binding the active ingredientsto solid carriers. Examples of solid carriers are mineral earths such assilica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk,bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate,magnesium sulfate, magnesium oxide, ground synthetic materials,fertilizers, such as, for example, ammonium sulfate, ammonium phosphate,ammonium nitrate, ureas, and products of vegetable origin, such ascereal meal, tree bark meal, wood meal and nutshell meal, cellulosepowders and other solid carriers.

In general, the formulations comprise from 0.01 to 95% by weight,preferably from 0.1 to 90% by weight, of the active ingredient. Theactive ingredients are employed in a purity of from 90% to 100%,preferably 95% to 100% (according to NMR spectrum).

The following are examples of formulations:

1. Products for Dilution with Water

A Soluble concentrates (SL, LS)

10 parts by weight of a compound according to the invention aredissolved in water or in a water-soluble solvent. As an alternative,wetters or other auxiliaries are added. The active ingredient dissolvesupon dilution with water.

B Dispersible concentrates (DC)

20 parts by weight of a compound according to the invention aredissolved in cyclohexanone with addition of a dispersant, for examplepolyvinylpyrrolidone. Dilution with water gives a dispersion.

C Emulsifiable concentrates (EC)

15 parts by weight of a compound according to the invention aredissolved in xylene with addition of calcium dodecylbenzenesulfonate andcastor oil ethoxylate (in each case 5% strength). Dilution with watergives an emulsion.

D Emulsions (EW, EO, ES)

40 parts by weight of a compound according to the invention aredissolved in xylene with addition of calcium dodecylbenzenesulfonate andcastor oil ethoxylate (in each case 5% strength). This mixture isintroduced into water by means of an emulsifier (Ultraturrax) and madeinto a homogeneous emulsion. Dilution with water gives an emulsion.

E Suspensions (SC, OD, FS)

In an agitated ball mill, 20 parts by weight of a compound according tothe invention are milled with addition of dispersant, wetters and wateror an organic solvent to give a fine active ingredient suspension.Dilution with water gives a stable suspension of the active ingredient.

F Water-dispersible granules and water-soluble granules (WG, SG)

50 parts by weight of a compound according to the invention are groundfinely with addition of dispersants and wetters and made intowater-dispersible or water-soluble granules by means of technicalappliances (for example extrusion, spray tower, fluidized bed). Dilutionwith water gives a stable dispersion or solution of the activeingredient.

G Water-dispersible powders and water-soluble powders (WP, SP, WS)

75 parts by weight of a compound according to the invention are groundin a rotor-stator mill with addition of dispersant, wetters and silicagel. Dilution with water gives a stable dispersion or solution with theactive ingredient.

2. Products to be Applied Undiluted

H Dustable powders (DP, DS)

5 parts by weight of a compound according to the invention are groundfinely and mixed intimately with 95% of finely divided kaolin. Thisgives a dustable product.

I Granules (GR, FG, GG, MG)

0.5 parts by weight of a compound according to the invention is groundfinely and associated with 95.5% carriers. Current methods areextrusion, spray drying or the fluidized bed. This gives granules to beapplied undiluted.

J ULV solutions (UL)

10 parts by weight of a compound according to the invention aredissolved in an organic solvent, for example xylene. This gives aproduct to be applied undiluted.

The active ingredients can be used as such, in the form of theirformulations or the use forms prepared therefrom, eg. in the form ofdirectly sprayable solutions, powders, gels, suspensions or dispersions,emulsions, oil dispersions, pastes, dustable products, materials forspreading, or granules, microcapsules (CS), pellets or tablets, by meansof spraying, atomizing, dusting, spreading or pouring. The use formsdepend entirely on the intended purposes; it is intended to ensure ineach case the finest possible distribution of the active ingredientsaccording to the invention.

Aqueous use forms can be prepared from emulsion concentrates, pastes orwettable powders (sprayable powders, oil dispersions) by adding water.To prepare emulsions, pastes or oil dispersions, the substances, as suchor dissolved in an oil or solvent, can be homogenized in water by meansof a wetter, tackifier, dispersant or emulsifier. Alternatively, it ispossible to prepare concentrates composed of active substance, wetter,tackifier, dispersant or emulsifier and, if appropriate, solvent or oil,and such concentrates are suitable for dilution with water.

The active ingredient concentrations in the ready-to-use products can bevaried within relatively wide ranges. In general, they are from 0.0001to 10%, preferably from 0.01 to 1%.

The active ingredients may also be used successfully in theultra-low-volume process (ULV), it being possible to apply formulationscomprising over 95% by weight of active ingredient, or even to apply theactive ingredient without additives.

Various types of oils, wetters, adjuvants, herbicides, fungicides, otherpesticides, or bactericides may be added to the active ingredients, ifappropriate just immediately prior to use (tank mix). These agentsusually are admixed with the agents according to the invention in aweight ratio of 1:10 to 10:1.

The compounds of formula I are effective through both contact (via soil,glass, wall, bed net, carpet, plant parts or animal parts), andingestion (bait, or plant part) and through trophallaxis and transfer.

Preferred application methods are into water bodies, via soil, cracksand crevices, pastures, manure piles, sewers, into water, on floor,wall, or by perimeter spray application and bait.

According to a preferred embodiment of the invention, the compounds offormula I are employed via soil application. Soil application isespecially favorable for use against ants, termites, flies, crickets, orcockroaches.

According to another preferred embodiment of the invention, for useagainst non crop pests such as ants, termites, wasps, flies, mosquitoes,crickets, locusts, or cockroaches the compounds of formula I areprepared into a bait preparation.

The bait can be a liquid, a solid or a semisolid preparation (e.g. agel). Solid baits can be formed into various shapes and forms suitableto the respective application e.g. granules, blocks, sticks, disks.Liquid baits can be filled into various devices to ensure properapplication, e.g. open containers, spray devices, droplet sources, orevaporation sources. Gels can be based on aqueous or oily matrices andcan be formulated to particular necessities in terms of stickiness,moisture retention or aging characteristics.

The bait employed in the composition is a product which is sufficientlyattractive to incite insects such as ants, termites, wasps, flies,mosquitoes, crickets etc. or cockroaches to eat it. This attractant maybe chosen from feeding stimulants or para and/or sex pheromones.Suitable feeding stimulants are chosen, for example, from animal and/orplant proteins (meat-, fish- or blood meal, insect parts, cricketspowder, egg yolk), from fats and oils of animal and/or plant origin, ormono-, oligo- or polyorgano-saccharides, especially from sucrose,lactose, fructose, dextrose, glucose, starch, pectin or even molasses orhoney, or from salts such as ammonium sulfate, ammonium carbonate orammonium acetate. Fresh or decaying parts of fruits, crops, plants,animals, insects or specific parts thereof can also serve as a feedingstimulant. Pheromones are known to be more insect specific. Specificpheromones are described in the literature and are known to thoseskilled in the art.

Formulations of compounds of formula I as aerosols (e.g in spray cans),oil sprays or pump sprays are highly suitable for the non-professionaluser for controlling pests such as flies, fleas, ticks, mosquitoes,locusts or cockroaches. Aerosol recipes are preferably composed of theactive compound, solvents such as lower alcohols (e.g. methanol,ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethylketone), paraffin hydrocarbons (e.g. kerosenes) having boiling ranges ofapproximately 50 to 250° C., dimethylfomaamide, N-methylpyrrolidone,dimethyl sulphoxide, aromatic hydrocarbons such as toluene, xylene,water, furthermore auxiliaries such as emulsifiers such as sorbitolmonooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fattyalcohol ethoxylate, perfume oils such as ethereal oils, esters of mediumfatty acids with lower alcohols, aromatic carbonyl compounds, ifappropriate stabilizers such as sodium benzoate, amphoteric surfactants,lower epoxides, triethyl orthoformate and, if required, propellants suchas propane, butane, nitrogen, compressed air, dimethyl ether, carbondioxide, nitrous oxide, or mixtures of these gases.

The oil spray formulations differ from the aerosol recipes in that nopropellants are used.

The compounds of formula I and its respective compositions can also beused in mosquito coils and fumigating coils, smoke cartridges, vaporizerplates or long-term vaporizers and also in moth papers, moth pads orother heat-independent vaporizer systems.

Methods to control infectious diseases transmitted by insects (e.g.malaria, dengue and yellow fever, lymphatic filariasis, andleishmaniasis) with compounds of formula I and its respectivecompositions also comprise treating surfaces of huts and houses, airspraying and impregnation of curtains, tents, clothing items, bed nets,tsetse-fly trap or the like. Insecticidal compositions for applicationto fibers, fabric, knitgoods, nonwovens, netting material or foils andtarpaulins preferably comprise a mixture including the insecticide,optionally a repellent and at least one binder.

The impregnation of curtains and bednets is mostly done by dipping thetextile material into emulsions or dispersions of the insecticide orspraying them onto the nets.

The compounds of formula I are also suitable for the protection of theseed and the seedlings' roots and shoots, preferably the seeds, againstsoil pests.

Especially preferred is the protection of seeds from the group ofcereals (e.g. wheat, barley, rye), canola, sugar beet, maize, sorghum,sunflower, cotton, rice, peas, colza, potato, and market-garden cropslike rice, wheat, barley, or rye.

Conventional seed treatment formulations include for example flowableconcentrates FS, solutions LS, powders for dry treatment DS, waterdispersible powders WS or granules for slurry treatment, water solublepowders SS and emulsion ES. Application to the seeds is carried outbefore sowing, either directly on the seeds or after havingpregerminated the latter.

Preferred are FS formulations.

Preferred FS formulations of compounds of formula I for seed treatmentcomprise from 0.5 to 80% of the active ingredient, from 0.05 to 5% of awetter, from 0.5 to 15% of a dispersing agent, from 0.1 to 5% of athickener, from 5 to 20% of an anti-freeze agent, from 0.1 to 2% of ananti-foam agent, from 1 to 20% of a pigment and/or a dye, from 0 to 15%of a sticker/adhesion agent, from 0 to 75% of a filler/vehicle, and from0.01 to 1% of a preservative.

In the treatment of seed, the application rates of the compound offormula I or compositions comprising it are generally from 0.1 g to 10kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed,in particular from 1 g to 2.5 kg per 100 kg of seed. For specific cropssuch as lettuce the rate can be higher.

In the control of pests, the application of the compound of formula I orof the composition comprising it is carried out by spraying or dustingthe seeds, the plants or the soil (and thereby the seeds) before orafter sowing of the plants or before or after emergence of the plants.

A further subject of the invention is a method of treating the seed inthe seed drill with a granular formulation containing the activeingredient or a composition comprising it, with optionally one or moresolid or liquid, agriculturally acceptable carriers and/or optionallywith one or more agriculturally acceptable surfactants. This method isadvantageously employed in seedbeds of cereal, maize, cotton andsunflower. For cereals and maize, the rates for compounds of formula Iare between 50 and 500 g/ha.

The invention also relates to the propagation product of plants, andespecially the treated seed comprising, that is, coated with and/orcontaining, a compound of formula I or a composition comprising it. Theterm “coated with and/or containing” generally signifies that the activeingredient is for the most part on the surface of the propagationproduct at the time of application, although a greater or lesser part ofthe ingredient may penetrate into the propagation product, depending onthe method of application. When the said propagation product is(re)planted, it may absorb the active ingredient.

The seed comprises the inventive compounds or compositions comprisingthem in an amount of from 0.1 g to 10 kg per 100 kg of seed.

Compositions of this invention may also contain other activeingredients, for example other pesticides, insecticides, herbicides,fertilizers such as ammonium nitrate, urea, potash, and superphosphate,phytotoxicants and plant growth regulators, safeners and nematicides.These additional ingredients may be used sequentially or in combinationwith the above-described compositions, if appropriate also added onlyimmediately prior to use (tank mix). For example, the plant(s) may besprayed with a composition of this invention either before or afterbeing treated with other active ingredients.

The following list of pesticides together with which the compoundsaccording to the invention can be used, is intended to illustrate thepossible combinations, but not to impose any limitation:

A.1. Organo(thio)phosphates: acephate, azamethiphos, azinphos-methyl,chlorpyrifos, chlorpyrifos-methyl, chlorfenvinphos, diazinon,dichlorvos, dicrotophos, dimethoate, disulfoton, ethion, fenitrothion,fenthion, isoxathion, malathion, methamidophos, methidathion,methyl-parathion, mevinphos, monocrotophos, oxydemeton-methyl, paraoxon,parathion, phenthoate, phosalone, phosmet, phosphamidon, phorate,phoxim, pirimiphos-methyl, profenofos, prothiofos, sulprophos,tetrachlorvinphos, terbufos, triazophos, trichlorfon;

A.2. Carbamates: alanycarb, aldicarb, bendiocarb, benfuracarb, carbaryl,carbofuran, carbosulfan, fenoxycarb, furathiocarb, methiocarb, methomyl,oxamyl, pirimicarb, propoxur, thiodicarb, triazamate;

A.3. Pyrethroids: allethrin, bifenthrin, cyfluthrin, cyhalothrin,cyphenothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin,zeta-cypermethrin, deltamethrin, esfenvalerate, etofenprox,fenpropathrin, fenvalerate, imiprothrin, lambda-cyhalothrin, permethrin,prallethrin, pyrethrin I and II, resmethrin, silafluofen,tau-fluvalinate, tefluthrin, tetramethrin, tralomethrin, transfluthrin,profluthrin, dimefluthrin;

A.4. Growth regulators: a) chitin synthesis inhibitors: benzoylureas:chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron,hexaflumuron, lufenuron, novaluron, teflubenzuron, triflumuron;buprofezin, diofenolan, hexythiazox, etoxazole, clofentazine; b)ecdysone antagonists: halofenozide, methoxyfenozide, tebufenozide,azadirachtin; c) juvenoids: pyriproxyfen, methoprene, fenoxycarb; d)lipid biosynthesis inhibitors: spirodiclofen, spiromesifen,spirotetramat;

A.5. Nicotinic receptor agonists/antagonists compounds: clothianidin,dinotefuran, imidacloprid, thiamethoxam, nitenpyram, acetamiprid,thiacloprid; the thiazol compound of formula Γ¹

A.6. GABA antagonist compounds: acetoprole, endosulfan, ethiprole,fipronil, vaniliprole, pyrafluprole, pyriprole, the phenylpyrazolecompound of formula Γ²

A.7. Macrocyclic lactone insecticides: abamectin, emamectin,milbemectin, lepimectin, spinosad,

A.8. METI I compounds: fenazaquin, pyridaben, tebufenpyrad, tolfenpyrad,flufenerim;

A.9. METI II and III compounds: acequinocyl, fluacyprim, hydramethyinon;

A.10. Uncoupler compounds: chlorfenapyr;

A.11. Oxidative phosphorylation inhibitor compounds: cyhexatin,diafenthiuron, fenbutatin oxide, propargite;

A.12. Moulting disruptor compounds: cyromazine;

A.13. Mixed Function Oxidase inhibitor compounds: piperonyl butoxide;

A.14. Sodium channel blocker compounds: indoxacarb, metaflumizone,

A.15. Various: benclothiaz, bifenazate, cartap, flonicamid, pyridalyl,pymetrozine, sulfur, thiocyclam, flubendiamide, cyenopyrafen,flupyrazofos, cyflumetofen, amidoflumet, the aminoisothiazole compoundsof formula Γ³,

wherein R^(i) is —CH₂OCH₂CH₃ or H and R^(ii) is CF₂CF₂CF₃ orCH₂CH(CH₃)₃, the anthranilamide compounds of formula Γ⁴

wherein A¹ is CH₃, Cl, Br, I, X is C—H, C—Cl, C—F or N, Y′ is F, Cl, orBr, Y″ is hydrogen, F, Cl, CF₃, B¹ is hydrogen, Cl, Br, I, CN, B² is Cl,Br, CF₃, OCH₂CF₃, OCF₂H, and R^(B) is hydrogen, CH₃ or CH(CH₃)₂, and themalononitrile compounds as described in JP 2002 284608, WO 02/89579, WO02/90320, WO 02/90321, WO 04/06677, WO 04/20399, JP 2004 99597, WO05/68423, WO 05/68432, or WO 05/63694, especially the malononitrilecompounds CF₂HCF₂CF₂CF₂CH₂C(CN)₂CH₂CH₂CF₃(2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,3-trifluoropropyl)malononitrile),CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₅CF₂H(2-(2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoro-heptyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₃(CH₂)₂C(CN)₂(CH₂)₂C(CF₃)₂F(2-(3,4,4,4-Tetrafluoro-3-trifluoromethyl-butyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₃(CH₂)₂C(CN)₂(CH₂)₂(CF₂)₃CF₃(2-(3,3,4,4,5,5,6,6,6-Nonafluoro-hexyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₂H(CF₂)₃CH₂C(CN)₂CH₂(CF₂)₃CF₂H(2,2-Bis-(2,2,3,3,4,4,5,5-octafluoro-pentyl)-malononitrile),CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₃CF₃(2-(2,2,3,3,4,4,5,5,5-Nonafluoro-pentyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₃(CF₂)₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H(2-(2,2,3,3,4,4,4-Heptafluoro-butyl)-2-(2,2,3,3,4,4,5,5-octafluoro-pentyl)-malononitrile)and CF₃CF₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H(2-(2,2,3,3,4,4,5,5-Octafluoro-pentyl)-2-(2,2,3,3,3-pentafluoro-propyl)-malononitrile).

The commercially available compounds of the group A may be found in ThePesticide Manual, 13^(th) Edition, British Crop Protection Council(2003) among other publications. Thiamides of formula Γ² and theirpreparation have been described in WO 98/28279. Aminoisothiazolecompounds of formula Γ³ and their preparation have been described in WO00/06566. Lepimectin is known from Agro Project, PJB Publications Ltd,November 2004. Benclothiaz and its preparation have been described inEP-A1 454621. Methidathion and Paraoxon and their preparation have beendescribed in Farm Chemicals Handbook, Volume 88, Meister PublishingCompany, 2001. Acetoprole and its preparation have been described in WO98/28277. Metaflumizone and its preparation have been described in EP-A1462 456. Flupyrazofos has been described in Pesticide Science 54, 1988,p.237-243 and in U.S. Pat. No. 4,822,779. Pyrafluprole and itspreparation have been described in JP 2002193709 and in WO 01/00614.Pyriprole and its preparation have been described in WO 98/45274 and inU.S. Pat. No. 6,335,357. Amidoflumet and its preparation have beendescribed in U.S. Pat. No. 6,221,890 and in JP 21010907. Flufenerim andits preparation have been described in WO 03/007717 and in WO 03/007718.Cyflumetofen and its preparation have been described in WO 04/080180.Anthranilamides of formula Γ⁴ and their preparation have been describedin WO 01/70671; WO 02/48137; WO 03/24222, WO 03/15518, WO 04/67528; WO04/33468; and WO 05/118552. The malononitrile compoundsCF₂HCF₂CF₂CF₂CH₂C(CN)₂CH₂CH₂CF₃(2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,3-trifluoropropyl)malononitrile),CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₅CF₂H(2-(2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoro-heptyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₃(CH₂)₂C(CN)₂(CH₂)₂C(CF₃)₂F(2-(3,4,4,4-Tetrafluoro-3-trifluoromethyl-butyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₃(CH₂)₂C(CN)₂(CH₂)₂(CF₂)₃CF₃(2-(3,3,4,4,5,5,6,6,6-Nonafluoro-hexyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₂H(CF₂)₃CH₂C(CN)₂CH₂(CF₂)₃CF₂H(2,2-Bis-(2,2,3,3,4,4,5,5-octafluoro-pentyl)-malononitrile),CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₃CF₃(2-(2,2,3,3,4,4,5,5,5-Nonafluoro-pentyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₃(CF₂)₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H(2-(2,2,3,3,4,4,4-Heptafluoro-butyl)-2-(2,2,3,3,4,4,5,5-octafluoro-pentyl)-malononitrile)and CF₃CF₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H(2-(2,2,3,3,4,4,5,5-Octafluoro-pentyl)-2-(2,2,3,3,3-pentafluoro-propyl)-malononitrile)have been described in WO 05/63694.

Preferred are mixtures withN-R′-2,2-dihalo-1-R″cyclo-propanecarboxamide-2-(2,6-dichloro-α,α,α-tri-fluoro-p-tolyl)hydrazoneorN-R′-2,2-di(R′″)propionamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)-hydrazone,wherein R′ is methyl or ethyl, halo is chloro or bromo, R″ is hydrogenor methyl and R′″ is methyl or ethyl.

Some of the mixtures of the compounds of formula I with theabove-mentioned pesticides are synergistic, that is, they contain theactive mixing partner in synergistically effective amounts. Synergisticmixtures of compounds of formula I with the following pesticides arepreferred:

Moreover, especially preferred with regard to their use according to thepresent invention are mixtures wherein the compound of formula II isselected from the groups A.3. (pyrethroids), A.4. (growth regulators),A.5. (nicotinic receptor agonists/antagonists compounds), A.6. (GABAantagonist compounds), A.7. (macrocyclic lactone insecticides),A.10.(uncoupler compounds), A.14. (sodium channel blocker compounds), orA.15. (various pesticide compounds).

Most preferred are mixtures wherein the compound of formula II isselected from the group A-1 consisting of bifenthrin, cyhalothrin,cypermethrin, alpha-cypermethrin, deltamethrin, lamda-cyhalothrin,permethrin; flufenoxuron, hexaflumuron, teflubenzuron, novaluron;clothianidin, acetamiprid, imidacloprid, thiamethoxam; fipronil,ethiprole; abmamectin, emamectin, spinosad; chlorfenapyr; indoxacarb,metaflumizone; anthranilamide compounds of formula Γ⁴, malononitrilecompounds as described in JP 2002 284608, WO 02/89579, WO 02/90320, WO02/90321, WO 04/06677, WO 04/20399, JP 2004 99597, WO 05/68423, WO05/68432, or WO 05/63694, especially the malononitrile compoundsCF₂HCF₂CF₂CF₂CH₂C(CN)₂CH₂CH₂CF₃(2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,3-trifluoropropyl)malononitrile),CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₅CF₂H(2-(2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoro-heptyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₃(CH₂)₂C(CN)₂(CH₂)₂C(CF₃)₂F(2-(3,4,4,4-Tetrafluoro-3-trifluoromethyl-butyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₃(CH₂)₂C(CN)₂(CH₂)₂(CF₂)₃CF₃(2-(3,3,4,4,5,5,6,6,6-Nonafluoro-hexyl)-2-(3,3,3-trifluoro-propyl)-malononitrile),CF₂H(CF₂)₃CH₂C(CN)₂CH₂(CF₂)₃CF₂H(2,2-Bis-(2,2,3,3,4,4,5,5-octafluoro-pentyl)-malononitrile),CF₃(CH₂)₂C(CN)₂CH₂(CF₂)₃CF₃(2-(2,2,3,3,4,4,5,5,5-Nonafluoro-pentyl)-2-(3,3,3-trifluoro-propyl)-maiononitrile),CF₃(CF₂)₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H(2-(2,2,3,3,4,4,4-Heptafluoro-butyl)-2-(2,2,3,3,4,4,5,5-octafluoro-pentyl)-malononitrile) and CF₃CF₂CH₂C(CN)₂CH₂(CF₂)₃CF₂H(2-(2,2,3,3,4,4,5,5-Octafluoro-pentyl)-2-(2,2,3,3,3-pentafluoro-propyl)-malononitrile),pymetrazine, pyridalyl.

Synergistic mixtures of the compound of formula l:1-(2,6-dichloro-4-trifluoromethylphenyl)-3-(1-methyl-2,2-dichlorocyclopropyl)-5-methyl-1,2,4-triazolewith one of the pesticides of group A-1 below are especially preferred.

Also especially preferred are synergistic mixtures of the compound offormula I:1-(2,6-dichloro-4-trifluoromethylphenyl)-3-(2,2-dichlorocyclopropyl)-5-methyl-1,2,4-triazole.with one of the pesticides of group A-1 below are especially preferred.

The synergistic mixtures advantageously reduce the dosage rate and/orenhance the spectrum of activity and/or combine know-down activity withprolonged control and/or resistance management. They allow enhancedcontrol of pests compared to the control rates that are possible withthe individual compounds.

The mixtures of compounds I and II, or the compounds I and II usedsimultaneously, that is jointly or separately, or in succession, thesequence, in the case of separate application, generally not having anyeffect on the result of the control measures, exhibit outstanding actionagainst pests from the above-mentioned orders.

The compounds I and the compound II are usually applied in a weightratio of from 100:1 to 1:100, preferably from 20:1 to 1:50, inparticular from 5:1 to 1:20.

The synergistic mixtures according to the invention can be convertedinto the customary formulations as mentioned below for compounds offormula I. The ranges of the application rates also are as mentioned forcompounds of formula I.

The insects may be controlled by contacting the target parasite/pest,its food supply, habitat, breeding ground or its locus with apesticidally effective amount of compounds of or compositions of formulaI.

“Locus” means a habitat, breeding ground, plant, seed, soil, area,material or environment in which a pest or parasite is growing or maygrow.

In general, “pesticidally effective amount” means the amount of activeingredient needed to achieve an observable effect on growth, includingthe effects of necrosis, death, retardation, prevention, and removal,destruction, or otherwise diminishing the occurrence and activity of thetarget organism. The pesticidally effective amount can vary for thevarious compounds/compositions used in the invention. A pesticidallyeffective amount of the compositions will also vary according to theprevailing conditions such as desired pesticidal effect and duration,weather, target species, locus, mode of application, and the like.

The compounds of formula I and its compositions can be used forprotecting wooden materials such as trees, board fences, sleepers, etc.and buildings such as houses, outhouses, factories, but alsoconstruction materials, furniture, leathers, fibers, vinyl articles,electric wires and cables etc. from ants and/or termites, and forcontrolling ants and termites from doing harm to crops or human being(e.g. when the pests invade into houses and public facilities). Thecompounds of formula I are applied not only to the surrounding soilsurface or into the under-floor soil in order to protect woodenmaterials but it can also be applied to lumbered articles such assurfaces of the under-floor concrete, alcove posts, beams, plywoods,furniture, etc., wooden articles such as particle boards, half boards,etc. and vinyl articles such as coated electric wires, vinyl sheets,heat insulating material such as styrene foams, etc. In case ofapplication against ants doing harm to crops or human beings, the antcontrol composition of the present invention is directly applied to thenest of the ants or to its surrounding or via bait contact.

The compounds or compositions of the invention can also be appliedpreventively to places at which occurrence of the pests is expected.

The compounds of formula I may also be used to protect growing plantsfrom attack or infestation by pests by contacting the plant with apesticidally effective amount of compounds of formula I. As such,“contacting” includes both direct contact (applying thecompounds/compositions directly on the pest and/or plant—typically tothe foliage, stem or roots of the plant) and indirect contact (applyingthe compounds/compositions to the locus of the pest and/or plant).

In the case of soil treatment or of application to the pests dwellingplace or nest, the quantity of active ingredient ranges from 0.0001 to500 g per 100 m², preferably from 0.001 to 20 g per 100 m². Soiltreatment of termites (Isoptera) is an especially preferred embodimentof the present invention.

Customary application rates in the protection of materials are, forexample, from 0.01 g to 1000 g of active compound per m² treatedmaterial, desirably from 0.1 g to 50 g per m².

Insecticidal compositions for use in the impregnation of materialstypically contain from 0.001 to 95 weight %, preferably from 0.1 to 45weight %, and more preferably from 1 to 25 weight % of at least onerepellent and/or insecticide.

For use in bait compositions, the typical content of active ingredientis from 0.0001 weight % to 15 weight %, desirably from 0.001 weight % to5% weight % of active compound. The composition used may also compriseother additives such as a solvent of the active material, a flavoringagent, a preserving agent, a dye or a bitter agent. Its attractivenessmay also be enhanced by a special color, shape or texture.

For use in spray compositions, the content of active ingredient is from0.001 to 80 weights %, preferably from 0.01 to 50 weight % and mostpreferably from 0.01 to 15 weight %.

For use in treating crop plants, the rate of application of the activeingredients of this invention may be in the range of 0.1 g to 4000 g perhectare, desirably from 25 g to 600 g per hectare, more desirably from50 g to 500 g per hectare.

Compounds of formula I and compositions comprising them can also be usedfor controlling and preventing infestations and infections animalsincluding warm-blooded animals (including humans) and fish. They are forexample suitable for controlling and preventing infestations andinfections in mammals such as cattle, sheep, swine, camels, deer,horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo,donkeys, fallow deer and reindeer, and also in fur-bearing animals suchas mink, chinchilla and raccoon, birds such as hens, geese, turkeys andducks and fish such as fresh- and salt-water fish such as trout, carpand eels.

Compounds of formula I and compositions comprising them are preferablyused for controlling and preventing infestations and infections indomestic animals, such as dogs or cats.

Infestations in warm-blooded animals and fish include, but are notlimited to, lice, biting lice, ticks, nasal bots, keds, biting flies,muscoid flies, flies, myiasitic fly larvae, chiggers, gnats, mosquitoesand fleas.

The compounds of formula I and compositions comprising them are suitablefor systemic and/or non-systemic control of ecto- and/or endoparasites.They are active against all or some stages of development.

The compounds of formula I are especially useful for combatingectoparasites.

The compounds of formula I are especially useful for combating parasitesof the following orders and species, respectively:

fleas (Siphonaptera), e.g. Ctenocephalides fells, Ctenocephalides canis,Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllusfasciatus,

cockroaches (Blaftaria—Blattodea), e.g. Blattella germanica, Blattellaasahinae, Periplaneta americana, Periplaneta japonica, Periplanetabrunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blaftaorientalis,

flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopicus, Aedesvexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians,Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anophelesleucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphoravicina, Chiysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria,Chrysops discalis, Chrysops silacea, Chrysops aflanticus, Cochliomylahominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pipiens,Culex nigripalpus, Culex quinquefasciatus, Culex tarsalls, Culisetainornata, Culiseta melanura, Dermatobia hominis, Fannia canicuiads,Gasterophilus intestinalis, Glossina morsitans, Glossina palpalis,Glossina fuscipes, Glossina tachinoides, Haematobia irritans,Haplodiplosis equestrds, Hippelates spp., Hypoderma lineata, Leptoconopstorrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoriapectoralis, Mansonia spp., Musca domestics, Muscina stabulans, Oestrusovis, Phlebotomus argentipes, Psorophora columbiae, Psorophora discolor,Prosimulium mixturn, Sarcophaga haemorrhoidalls, Sarcophaga sp.,Simullum vfttatum, Stomoxys calcitrans, Tabanus bovinus, Tabanusatratus, Tabanus lineola, and Tabanus similis,

lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanuscorporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis,Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthusstramineus and Solenopotes capillatus.

ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodesscapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalussanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyommaamerdcanum, Ambryomma macuiatum, Ornithodorus hermsi, Ornithodorusturicata and parasitic mites (Mesostigmata), e.g. Ornithonyssus bacoiand Dermanyssus gallnae, Actinedida (Prostigmata) and Acaridida(Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletiaspp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp.,Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp.,Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp.,Otodectes spp., Sarcoptes spp., Notoedres spp., Knemidocoptes spp.,Cytodites spp., and Laminosioptes spp,

Bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduviussenilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Ariluscrltatus,

Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp.,Phtirus spp., and Solenopotes spp,

Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenoponspp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp.,Lepikentron spp., Trichodectes spp., and Felicola spp,

Roundworms Nematoda:

Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae(Trichinella spp.), (Trichuridae) Trichuris spp., Capillaria spp,

Rhabditida, e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp,

Strongylida, e.g. Strongylus spp., Ancylostoma spp., Necator americanus,Bunostomum spp. (Hookworm), Trichostrongylus spp., Haemonchuscontortus., Ostertagia spp., Cooperia spp., Nematodirus spp.,Dictyocaulus spp., Cyathostoma spp., Oesophagostomum spp., Stephanurusdentatus, Ollulanus spp., Chabertia spp., Stephanurus dentatus, Syngamustrachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necatorspp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp.,Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylusabstrusus, and Dioctophyma renale,

Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascarissuum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis(Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., andOxyuris equi,

Camallanida, e.g. Dracunculus medinensis (guinea worm)

Spirurida, e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocercaspp., Dirofilari spp.a, Dipetalonema spp., Setaria spp., Elaeophoraspp., Spirocerca lupi, and Habronema spp.,

Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp.,Macracanthorhynchus hirudinaceus and Oncicola spp,

Planarians (Plathelminthes):

Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimusspp., Dicrocoellum spp., Fasciolopsis buski, Clonorchis sinensis,Schistosoma spp., Trichobllharzia spp., Alaria alata, Paragonimus spp.,and Nanocyetes spp,

Cercomeromorpha, in particular Cestoda (Tapeworms), e.g.Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidiumcaninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp.,Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp.,Anoplocephala spp., and Hymenolepis spp.

The compounds of formula I and compositions containing them areparticularly useful for the control of pests from the orders Diptera,Siphonaptera and Ixodida, especially for control of mosquitoes.

The use of the compounds of formula I and compositions containing themfor combating flies is a further preferred embodiment of the presentinvention.

Furthermore, the use of the compounds of formula I and compositionscontaining them for combating fleas is especially preferred.

The use of the compounds of formula I and compositions containing themfor combating ticks is a further preferred embodiment of the presentinvention.

The compounds of formula I also are especially useful for combatingendoparasites (roundworms nematoda, thorny headed worms and planarians).

Administration can be carried out both prophylactically andtherapeutically.

Administration of the active compounds is carried out directly or in theform of suitable preparations, orally, topically/dermally orparenterally.

For oral administration to warm-blooded animals, the formula I compoundsmay be formulated as animal feeds, animal feed premixes, animal feedconcentrates, pills, solutions, pastes, suspensions, drenches, gels,tablets, boluses and capsules. In addition, the formula I compounds maybe administered to the animals in their drinking water. For oraladministration, the dosage form chosen should provide the animal with0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula Icompound, preferably with 0.5 mg/kg to 100 mg/kg of animal body weightper day.

Alternatively, the formula I compounds may be administered to animalsparenterally, for example, by intraruminal, intramuscular, intravenousor subcutaneous injection. The formula I compounds may be dispersed ordissolved in a physiologically acceptable carrier for subcutaneousinjection. Alternatively, the formula I compounds may be formulated intoan implant for subcutaneous administration. In addition the formula Icompound may be transdermally administered to animals. For parenteraladministration, the dosage form chosen should provide the animal with0.01 mg/kg to 100 mg/kg of animal body weight per day of the formula Icompound.

The formula I compounds may also be applied topically to the animals inthe form of dips, dusts, powders, collars, medallions, sprays, shampoos,spot-on and pour-on formulations and in ointments or oil-in-water orwater-in-oil emulsions. For topical application, dips and sprays usuallycontain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of theformula I compound. In addition, the formula I compounds may beformulated as ear tags for animals, particularly quadrupeds such ascattle and sheep.

Suitable preparations are:

-   -   Solutions such as oral solutions, concentrates for oral        administration after dilution, solutions for use on the skin or        in body cavities, pouring-on formulations, gels;    -   Emulsions and suspensions for oral or dermal administration;        semi-solid preparations;    -   Formulations in which the active compound is processed in an        ointment base or in an oil-in-water or water-in-oil emulsion        base;    -   Solid preparations such as powders, premixes or concentrates,        granules, pellets, tablets, boluses, capsules; aerosols and        inhalants, and active compound-containing shaped articles.

Compositions suitable for injection are prepared by dissolving theactive ingredient in a suitable solvent and optionally adding furtheringredients such as acids, bases, buffer salts, preservatives, andsolubilizers. The solutions are filtered and filled sterile.

Suitable solvents are physiologically tolerable solvents such as water,alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propyleneglycol, polyethylene glycols, N-methyl-pyrrolidone, 2-pyrrolidone, andmixtures thereof.

The active compounds can optionally be dissolved in physiologicallytolerable vegetable or synthetic oils which are suitable for injection.

Suitable solubilizers are solvents which promote the dissolution of theactive compound in the main solvent or prevent its precipitation.Examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylatedcastor oil, and polyoxyethylated sorbitan ester.

Suitable preservatives are benzyl alcohol, trichlorobutanol,p-hydroxybenzoic acid esters, and n-butanol.

Oral solutions are administered directly. Concentrates are administeredorally after prior dilution to the use concentration. Oral solutions andconcentrates are prepared according to the state of the art and asdescribed above for injection solutions, sterile procedures not beingnecessary.

Solutions for use on the skin are trickled on, spread on, rubbed in,sprinkled on or sprayed on.

Solutions for use on the skin are prepared according to the state of theart and according to what is described above for injection solutions,sterile procedures not being necessary.

Further suitable solvents are polypropylene glycol, phenyl ethanol,phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate,ethers such as alkyleneglycol alkylether, e.g. dipropylenglycolmonomethylether, ketons such as acetone, methylethylketone, aromatichydrocarbons, vegetable and synthetic oils, dimethylformamide,dimethylacetamide, transcutol, solketal, propylencarbonate, and mixturesthereof.

It may be advantageous to add thickeners during preparation. Suitablethickeners are inorganic thickeners such as bentonites, colloidalsilicic acid, aluminium monostearate, organic thickeners such ascellulose derivatives, polyvinyl alcohols and their copolymers,acrylates and methacrylates.

Gels are applied to or spread on the skin or introduced into bodycavities. Gels are prepared by treating solutions which have beenprepared as described in the case of the injection solutions withsufficient thickener that a clear material having an ointment-likeconsistency results. The thickeners employed are the thickeners givenabove.

Pour-on formulations are poured or sprayed onto limited areas of theskin, the active compound penetrating the skin and acting systemically.

Pour-on formulations are prepared by dissolving, suspending oremulsifying the active compound in suitable skin-compatible solvents orsolvent mixtures. If appropriate, other auxiliaries such as colorants,bioabsorption-promoting substances, antioxidants, light stabilizers,adhesives are added.

Suitable solvents which are: water, alkanols, glycols, polyethyleneglycols, polypropylene glycols, glycerol, aromatic alcohols such asbenzyl alcohol, phenylethanol, phenoxyethanol, esters such as ethylacetate, butyl acetate, benzyl benzoate, ethers such as alkylene glycolalkyl ethers such as dipropylene glycol monomethyl ether, diethyleneglycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone,cyclic carbonates such as propylene carbonate, ethylene carbonate,aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils,DMF, dimethylacetamide, n-alkylpyrrolidones such as methylpyrrolidone,n-butylpyrrolidone or n-octylpyrrolidone, N-methylpyrrolidone,2-pyrrolidone, 2,2-dimethyl-4-oxy-methylene-1,3-diox-olane and glycerolformal.

Suitable colorants are all colorants permitted for use on animals andwhich can be dissolved or suspended.

Suitable absorption-promoting substances are, for example, DMSO,spreading oils such as isopropyl myristate, dipropylene glycolpelargonate, silicone oils and copolymers thereof with polyethers, fattyacid esters, triglycerides, fatty alcohols.

Suitable antioxidants are sulfites or metabisulfites such as potassiummetabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole,tocopherol.

Suitable light stabilizers are, for example, novantisolic acid.

Suitable adhesives are, for example, cellulose derivatives, starchderivatives, polyacrylates, natural polymers such as alginates, gelatin.

Emulsions can be administered orally, dermally or as injections.

Emulsions are either of the water-in-oil type or of the oil-in-watertype.

They are prepared by dissolving the active compound either in thehydrophobic or in the hydrophilic phase and homogenizing this with thesolvent of the other phase with the aid of suitable emulsifiers and, ifappropriate, other auxiliaries such as colorants, absorption-promotingsubstances, preservatives, antioxidants, light stabilizers,viscosity-enhancing substances.

Suitable hydrophobic phases (oils) are:

-   -   liquid paraffins, silicone oils, natural vegetable oils such as        sesame oil, almond oil, castor oil, synthetic triglycerides such        as caprylic/capric biglyceride, triglyceride mixture with        vegetable fatty acids of the chain length C₈-C₁₂ or other        specially selected natural fatty acids, partial glyceride        mixtures of saturated or unsaturated fatty acids possibly also        containing hydroxyl groups, mono- and diglycerides of the C₈-C₁₀        fatty acids,    -   fatty acid esters such as ethyl stearate, di-n-butyryl adipate,        hexyl laurate, dipropylene glycol perlargonate, esters of a        branched fatty acid of medium chain length with saturated fatty        alcohols of chain length C16-C₁₈, isopropyl myristate, isopropyl        palmitate, caprylic/capric acid esters of saturated fatty        alcohols of chain length C₁₂-C₁₈, isopropyl stearate, oleyl        oleate, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty        acid esters such as synthetic duck coccygeal gland fat, dibutyl        phthalate, diisopropyl adipate, and ester mixtures related to        the latter,    -   fatty alcohols such as isotridecyl alcohol, 2-octyldodecanol,        cetylstearyl alcohol, oleyl alcohol, and    -   fatty acids such as oleic acid and    -   mixtures thereof.

Suitable hydrophilic phases are: water, alcohols such as propyleneglycol, glycerol, sorbitol and mixtures thereof.

Suitable emulsifiers are:

-   -   non-ionic surfactants, e.g. polyethoxylated castor oil,        polyethoxylated sorbitan monooleate, sorbitan monostearate,        glycerol monostearate, polyoxyethyl stearate, alkylphenol        polyglycol ether;    -   ampholytic surfactants such as di-sodium        N-lauryl-p-iminodipropionate or lecithin;    -   anionic surfactants, such as sodium lauryl sulfate, fatty        alcohol ether sulfates, mono/dialkyl polyglycol ether        orthophosphoric acid ester monoethanolamine salt;    -   cation-active surfactants, such as cetyltrimethylammonium        chloride.

Suitable further auxiliaries are: substances which enhance the viscosityand stabilize the emulsion, such as carboxymethylcellulose,methyicellulose and other cellulose and starch derivatives,polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone,polyvinyl alcohol, copolymers of methyl vinyl ether and maleicanhydride, polyethylene glycols, waxes, colloidal silicic acid ormixtures of the substances mentioned.

Suspensions can be administered orally or topically/dermally. They areprepared by suspending the active compound in a suspending agent, ifappropriate with addition of other auxiliaries such as wetting agents,colorants, bioabsorption-promoting substances, preservatives,antioxidants, light stabilizers.

Liquid suspending agents are all homogeneous solvents and solventmixtures.

Suitable wetting agents (dispersants) are the emulsifiers given above.

Other auxiliaries which may be mentioned are those given above.

Semi-solid preparations can be administered orally ortopically/dermally. They differ from the suspensions and emulsionsdescribed above only by their higher viscosity.

For the production of solid preparations, the active compound is mixedwith suitable excipients, if appropriate with addition of auxiliaries,and brought into the desired form.

Suitable excipients are all physiologically tolerable solid inertsubstances. Those used are inorganic and organic substances. Inorganicsubstances are, for example, sodium chloride, carbonates such as calciumcarbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicicacids, argillaceous earths, precipitated or colloidal silica, orphosphates. Organic substances are, for example, sugar, cellulose,foodstuffs and feeds such as milk powder, animal meal, grain meals andshreds, starches.

Suitable auxiliaries are preservatives, antioxidants, and/or colorantswhich have been mentioned above.

Other suitable auxiliaries are lubricants and glidants such as magnesiumstearate, stearic acid, talc, bentonites, disintegration-promotingsubstances such as starch or crosslinked polyvinylpyrrolidone, binderssuch as starch, gelatin or linear polyvinylpyrrolidone, and dry binderssuch as microcrystalline cellulose.

The compositions which can be used in the invention can comprisegenerally from about 0.001 to 95% of the compound of formula I.

Generally it is favorable to apply the compounds of formula I in totalamounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50mg/kg per day.

Ready-to-use preparations contain the compounds acting againstparasites, preferably ectoparasites, in concentrations of 10 ppm to 80percent by weight, preferably from 0.1 to 65 percent by weight, morepreferably from 1 to 50 percent by weight, most preferably from 5 to 40percent by weight.

Preparations which are diluted before use contain the compounds actingagainst ectoparasites in concentrations of 0.5 to 90 percent by weight,preferably of 1 to 50 per cent by weight.

Furthermore, the preparations comprise the compounds of formula Iagainst endoparasites in concentrations of 10 ppm to 2 percent byweight, preferably of 0.05 to 0.9 per cent by weight, very particularlypreferably of 0.005 to 0.25 percent by weight.

In a preferred embodiment of the present invention, the compositionscomprising the compounds of formula I them are applieddermally/topically.

In a further preferred embodiment, the topical application is conductedin the form of compound-containing shaped articles such as collars,medallions, ear tags, bands for fixing at body parts, and adhesivestrips and foils.

Generally it is favorable to apply solid formulations which releasecompounds of formula I in total amounts of 10 mg/kg to 300 mg/kg,preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kgbody weight of the treated animal in the course of three weeks.

For the preparation of the shaped articles, thermoplastic and flexibleplastics as well as elastomers and thermoplastic elastomers are used.Suitable plastics and elastomers are polyvinyl resins, polyurethane,polyacrylate, epoxy resins, cellulose, cellulose derivatives, polyamidesand polyester which are sufficiently compatible with the compounds offormula I. A detailed list of plastics and elastomers as well aspreparation procedures for the shaped articles is given e.g. in WO03/086075.

The active compounds can also be used as a mixture with synergists orwith other active compounds which act against pathogenic endo- andectoparasites. The following list of pesticides together with which thecompounds according to the invention can be used for controlling andpreventing infestations and infections in warm-blooded animals and fish,is intended to illustrate the possible combinations, but not to imposeany limitation:

Organophosphates: Acephate, Chlorfenvinphos, Diazinon, Dichlorvos,Dicrotophos, Dimethoate, Ethion, Fenitrothion, Fenthion, Isoxathion,Malathion, Phenthoate, Phosalone, Phosmet, Phoxim, Pirimiphos-methyl,Profenofos, Prothiofos, Sulprophos, Triazophos, Trichlorfon, Quintiofos,Coumaphos, Chlorphoxim, Bromophos-ethyl,2,3-p-Dioxanedithiol-S,S-bis(O,O-diethylphosphorodithionat);

Carbamates: Alanycarb, Benfuracarb, Carbaryl, Carbosulfan, Fenoxycarb,Furathiocarb, Indoxacarb, Triazamate;

Pyrethroids: alpha-Cypermethrin, Deltamethrin, Ethofenprox, Fenvalerate,Cyhalothrin, Lambda-Cyhalothrin, Permethrin, Silafluofen,Tau-Fluvalinate, Tralomethrin, Zeta-Cypermethrin, Flumethrin, Cyfluthrinand its enantiomers and stereomers, Cypermethrin;

Arthropod growth regulators: a) chitin synthesis inhibitors:benzoylureas: Chlorfluazuron, Cyromazine, Diflubenzuron, Flucycloxuron,Flufenoxuron, Hexaflumuron, Lufenuron, Novaluron, Teflubenzuron,Triflumuron; Buprofezin, Diofenolan, Hexythiazox, Etoxazole,Clofentazine; b) ecdysone antagonists: Halofenozide, Methoxyfenozide,Tebufenozide; c) juvenoids: Pyriproxyfen, Methoprene, Fenoxycarb; d)lipid biosynthesis inhibitors: Spirodiclofen;

(Neo)nicotinoids: Acetamiprid, Clothianidin, Flonicamid, Imidacloprid,Nitenpyram, Thiacloprid, Thiamethoxam;

Synthetic coccidiosis compounds, polyetherantibiotics: Amprolium,Robenidin, Toltrazuril, Monensin, Salinomycin, Maduramicin, Lasalocid,Narasin, Semduramicin;

Various: Abamectin (Avermectins), Acequinocyl, Amitraz, Azadirachtin,Bifenazate, Bacillus thuringiensis, Bacillus subtills, Cartap,Chlorfenapyr, Chlordimeform, Cyromazine, Diafenthiuron, Dinetofuran,Diofenolan, Emamectin, Endosulfan, Epsiprantel, Ethiprole, Fenazaquin,Fipronil, Formetanate, Formetanate hydrochloride, Hydramethylnon,Indoxacarb, Metaflumizone,L-2,3,5,6-tetrahydro-6-phenyl-imidazothiazole, Levamisole, Milbemectin(Milbemycins), Moxidectin, Praziquantel, Pyrantel, Pyridaben,Pymetrozine, Selamectin, Spinosad, Sulfur, Tebufenpyrad, and Thiocyclam.

In general, “parasiticidally effective amount” means the amount ofactive ingredient needed to achieve an observable effect on growth,including the effects of necrosis, death, retardation, prevention, andremoval, destruction, or otherwise diminishing the occurrence andactivity of the target organism. The parasiticidally effective amountcan vary for the various compounds/compositions used in the invention. Aparasiticidally effective amount of the compositions will also varyaccording to the prevailing conditions such as desired parasiticidaleffect and duration, target species, mode of application, and the like.

SYNTHESIS EXAMPLES

The compounds I obtained according to the protocols shown in thesynthesis examples below together with their physical data are listed inTable I which follows.

Example 1 Preparation of3-(2,2-Dichloro-1-methyl-cyclopropyl)-1-(2,6-dichloro-4-trifluoromethyl-phenyl)-5-methyl-1H-[1,2,4]triazole

50 gN-[1-(2,2,-Dichloro-1-methyl-cyclopropyl)-ethylidene]-N′-(2,6-dichloro-4-trifluoro-methylphenyl)-hydrazineand 17.9 ml pyridine were dissolved in 1 L toluene. At 0-5° C., 51 g DDQwas added portionwise. After stirring at 25° C. for 12 hours, 1 L 5%NaOH solution was added, the mixture was extracted with ether and driedwith MgSO₄. Removal of the solvent gave 48.6 g of the above compound(mp. 107-116° C.).

TABLE I (I)

Physical data No. X Y A B (m.p.[° C.]/¹H-NMR(CDCl₃): d [ppm]) I-1 Cl CF₃CH₃ H 8.21 (s), 7.77 (s), 2.58 (d), 1.87 (s), 1.66 (d). I-2 Cl CF₃ H CH₃133-138 I-3 Cl CF₃ CH₃ CH₃ 107-116 Compound from EP 957 094 A Cl CF₃ H H8.20 (s), 7.76 (s), 3.10 (dd), 2.34 (t), 2.09 (dd).

Examples of Action Against Pests

Test Methodology

Examples of Action Against Pests and Parasites

1. Activity against Argentine ant (Linepithema humile), harvester ant(Pogonomyrmex californicus), acrobat ant (Crematogaster spp.), carpenterant (Camponotus floridanus), fire ant (Solenopsis invicta), house fly(Musca domestica), stable fly (Stomoxys calcitrans), flesh fly(Sarcophaga sp.), yellowfever mosquito (Aedes aegyptil), house mosquito(Culex quinquefasciatus), malaria mosquito (Anopheles albimanus), Germancockroach (Blattella Germanica), cat flea (Ctenocephalides felis), andbrown dog tick (Rhipicephalus sanguineus) via glass contact

Glass vials were treated with 0.5 ml of a solution of active ingredientin acetone and allowed to dry. Insects or ticks were placed into eachvial together with some food and moisture supply. The vials were kept at22° C. and were observed for treatment effects at various timeintervals.

In these tests, compound I-3 at a rate of 0.1 ppm showed 100% mortalityof Aedes aegypti at 24 hours after treatment.

Furthermore, compound I-3 at a rate of 5 ppm showed 100% mortality ofMusca domestilca and Blattella Germanica at 24 hours after treatment.

Furthermore, compound I-3 at a rate of 10 ppm showed 100% mortality ofCrematogaster spp. at 24 hours after treatment.

2. Activity against Argentine ant (Linepithema humile), acrobat ant(Crematogaster spp.), carpenter ant (Camponotus floridanus), fire ant(Solenopsis invicta), and eastern subterranean termite (Reticulitermesflavipes) via soil contact

For ants, tests were conducted in Petri dishes. A thin layer of 1% agarin water was dispensed into the dishes and Florida sandy soil was spreadover the agar. The active ingredient was dissolved in acetone anddispensed over the sand. Dishes were vented to evaporate the acetone,infested with ants, and covered. A 20% honey water solution was placedin each dish. The dishes were maintained at 22° C. and observed formortality at various time intervals.

For termites, a thin layer of 1% agar was dispensed into Petri dishes. Athin layer of pre-treated soil was spread over the agar. For soiltreatment, the active ingredient was diluted in acetone on aweight-to-weight basis and incorporated into the soil. Termite workerswere introduced into each dish. Filter paper served as a food source.Test dishes were held at about 25° C. Termites were observed daily formortality (dead or unable to stand upright and showing only weakmovement).

In these tests, compound I-3 at a rate of 1 weight % showed 100%mortality of Reticulitermes flavipes at 3 days after treatment.

Furthermore, compound I-3 at a rate of 10 ppm showed 100% mortality ofCamponotus floridanus at 24 hours after treatment.

3. Activity against Argentine ant (Linepithema humile), acrobat ant(Crematogaster spp.), carpenter ant (Camponotus floridanus), fire ant(Solenopsis invicta), house fly (Musca domestica), eastern subterraneantermite (Reticulitermes flavipes), Formosan subterranean termite(Coptotermes formosanus), and German cockroach (Blattella Germanica) viabait

For Argentine ant, acrobat ant, and carpenter ant, tests were conductedin Petri dishes. Baits were prepared with either honey/water solutionsor ground cat chow. Active ingredient in acetone was added to the bait.0.2 ml of treated honey water solution or 150 mg of treated cat chow,placed in a cap, was added to each dish. The dishes were covered andmaintained at a temperature of 22° C. The ants were observed formortality daily.

For the fire ants, corn grit was used as a bait matrix (0.1% activeingredient). Fire ant adults were placed into Petri dishes together withthe bait. The ants were observed for mortality daily.

For house flies, bait tests were conducted with adults aged 2-5 dayspost-emergence. Active ingredient in acetone was applied to a baitmatrix consisting of a mixture of powdered milk and sugar. House flieswere placed into bait jars which were held at about 22° C. and wereobserved at 4 hours after treatment for knockdown (death plus morbidity(unable to stay upright)).

For termites, active ingredient in acetone was applied to filter papers.% a.i. were calculated on basis of the weight of the filter paper.Bioassays were conducted with one treated filter and ca. 30 termiteworkers per test Petri dish. Test dishes were maintained at 25° C. andobserved daily for mortality (dead or moribund insects) or intoxication.

For cockroaches, boxes with ventilated lids were used as test arenas.The bait was prepared using ground cat chow, and the active ingredientin acetone was incorporated on a weight-to-weight ratio (0.03 grams ofbait per box). The boxes were maintained at 22° C. and observed dailyfor mortality of the cockroaches.

In these tests, compound I-3 at a rate of 0.005 weight % showed 100%mortality of Reticulitermes flavipes at three days after treatment.

4. Activity against yellowfever mosquito (Aedes aegyptii), housemosquito (Culex quinquefasciatus) and malaria mosquito (Anophelesalbimanus) larvae via water treatment

Well plates were used as test arenas. The active ingredient wasdissolved in acetone 30 and diluted with water to obtain theconcentrations needed. The final solutions containing appr. 1% acetonewere placed into each well. Approximately 10 mosquito larvae(4^(th)-instars) in 1 ml water were added to each well. Larvae were fedone drop of liver powder each day. The dishes were covered andmaintained at 22° C. Mortality was recorded daily and dead larvae andlive or dead pupae were removed daily. At the end of the test remaininglive larvae were recorded and percent mortality was calculated.

5. Activity against cotton aphid (aphis gossypii)

The active compounds were formulated in 50:50 acetone:water and 100 ppmKinetic™ surfactant.

Cotton plants at the cotyledon stage (one plant per pot) were infestedby placing a heavily infested leaf from the main colony on top of eachcotyledon. The aphids were allowed to transfer to the host plantovernight, and the leaf used to transfer the aphids was removed. Thecotyledons were dipped in the test solution and allowed to dry. After 5days, mortality counts were made.

In this test, compound I-3 at 300 ppm showed 100% mortality.

6. Activity against green peach aphid (Myzus persicae)

The active compounds were formulated in 50:50 acetone:water and 100 ppmKinetic™ surfactant.

Pepper plants in the 2^(nd) leaf-pair stage (variety ‘CaliforniaWonder’) were infested with approximately 40 laboratory-reared aphids byplacing infested leaf sections on top of the test plants. The leafsections were removed after 24 hr. The leaves of the intact plants weredipped into gradient solutions of the test compound and allowed to dry.Test plants were maintained under fluorescent light (24 hourphotoperiod) at about 25° C. and 20-40% relative humidity. Aphidmortality on the treated plants, relative to mortality on check plants,was determined after 5 days.

In this test, compound I-3 at 300 ppm showed 100% mortality, whereascompound A at 300 ppm show no effect.

7. Activity against bean aphid (aphis fabae)

The active compounds were formulated in 50:50 acetone:water and 100 ppmKinetic™ surfactant.

Nasturtium plants grown in Metro mix in the 1^(st) leaf-pair stage(variety ‘Mixed Jewle’) were infested with approximately 2-30laboratory-reared aphids by placing infested cut plants on top of thetest plants. The cut plants were removed after 24 hr. Each plant wasdipped into the test solution to provide complete coverage of thefoliage, stem, protruding seed surface and surrounding cube surface andallowed to dry in the fume hood. The treated plants were kept at about25° C. with continuous fluorescent light. Aphid mortality was determinedafter 3 days.

In this test, compounds I-1 and I-3 at 300 ppm showed 100% mortality,whereas compound A showed no effect.

8. Activity against silverleaf whitefly (bemisia argentifolii)

The active compounds were formulated in 50:50 acetone:water and 100 ppmKinetic™ surfactant.

Selected cotton plants were grown to the cotyledon state (one plant perpot). The cotyledons were dipped into the test solution to providecomplete coverage of the foliage and placed in a well-vented area todry. Each pot with treated seedling was placed in a plastic cup and 10to 12 whitefly adults (approximately 3-5 day old) were introduced. Theinsects were colleted using an aspirator and an 0.6 cm, non-toxic Tygon®tubing (R-3603) connected to a barrier pipette tip. The tip, containingthe collected insects, was then gently inserted into the soil containingthe treated plant, allowing insects to crawl out of the tip to reach thefoliage for feeding. The cups were covered with a reusable screened lid(150 micron mesh polyester screen PeCap from Tetko Inc). Test plantswere maintained in the holding room at about 25° C. and 20-40% relativehumidity for 3 days avoiding direct exposure to the fluorescent light(24 hour photoperiod) to prevent trapping of heat inside the cup.Mortality was assessed 3 days after treatment of the plants.

In this test, compounds I-1 and I-3 at 300 ppm showed 100% mortality.

9. Activity against brown planthopper (nilaparvata lugens)

The active compounds were formulated in 50:50 acetone:water. Potted riceseedlings were sprayed with 10 ml test solution, air dried, placed incages and inoculated with 10 adults. Percent mortality was recordedafter 24, 72 and 120 hours.

In this test, compounds I-1,1-2 and I-3 at 300 ppm showed 100%mortality.

10. Activity against cowpea aphid (aphis craccivora)

The active compounds were formulated in 50:50 acetone:water. Pottedcowpea plants colonized with 100-150 aphids of various stages weresprayed after the pest population has been recorded. Populationreduction was recorded after 24, 72, and 120 hours.

In this test, compounds I-1, I-2 and I-3 at 300 ppm showed 100%mortality, whereas compound A showed no effect.

11. Activity against diamond back moth (plutella xylostella)

The active compounds were formulated in 50:50 acetone:water and 0.1%(vol/vol) Alkamuls EL 620 surfactant. A 6 cm leaf disk of cabbage leaveswas dipped in the test solution for 3 seconds and allowed to air dry ina Petri plate lined with moist filter paper. The leaf disk wasinoculated with 10 third instar larvae and kept at 25-27° C. and 50-60%humidity for 3 days. Mortality was assessed after 72 h of treatment. Inthis test, compounds I-1 and I-3 at 300 ppm showed 100% mortality,whereas compound A showed no effect.

12. Pesticidal action of synergistic mixtures of compounds of formula I

Potato plants for Colorado potato beetle and two-leaf cotton plants fortobacco budworm were utilized for bioassays. Excised plant leaves weredipped into 1:1 acetone/water dilutions of the active compounds. Afterthe leaves had dried, they were individually placed onto water-moistenedfilter paper on the bottoms of Petri dishes. Each dish was infested with5-7 larvae and covered with a lid. Each treatment dilution wasreplicated 4 times. Test dishes were held at approximately 27° C. and60% humidity. Numbers of live and morbid larvae were assessed in eachdish at 5 days after treatment application, and percent mortality wascalculated.

To determine if an insecticidal mixture was synergistic, Limpel'sformula was used:E=X+Y−XY/100

-   E=Expected % mortality of the mixture-   X=% mortality of compound X, as measured independently-   Y=% mortality of compound Y, as measured independently

Synergism was evident if the % observed mortality for the mixture wasgreater than the % expected mortality.

TABLE 1 Activity of mixtures of compound I-3 with alpha-cypermethrinDose rate % Mortality of % Mortality of Active [ppm] Colorado PotatoBeetle Tobacco Budworm I-3 300 71.4 100 12.5 0 alpha- 0.06 17.5 7.2cypermethrin 0.03 0 I-3 + alpha- % mortality % mortality % mortality %mortality cypermethrin observed expected observed expected 300 + 0.0692.9 73.5 300 + 0.03 82.1 71.4 100 + 0.06 79.2 27.8 82.1 7.2 100 + 0.0317.9 0

1. A compound of formula (I)

wherein X is chloro or bromo; Y is chloro or trifluormethyl; and A and Bare hydrogen or methyl with the proviso that one of A or B must bemethyl; or the enantiomers or salts thereof.
 2. The compound of claim 1,wherein B is methyl and X is chloro.
 3. The compound of claim 1, whereinA is methyl and X is chloro.
 4. A compound:1-(2,6-dichloro-4-trifluoromethylphenyl)-3-(1-methyl-2,2-dichlorocyclopropyl)-5-methyl-1,2,4-triazole.5. A method for the control of insects or acarids comprising: contactingthe insect or acarid or their food supply, habitat or breeding groundswith a pesticidally effective amount of a composition or a compound offormula I:

wherein X is chloro or bromo; Y is chloro or trifluormethyl; and A and Bare hydrogen or methyl with the proviso that one of A or B must bemethyl; or the enantiomers or salts thereof; wherein said insects orsaid acarids are controlled.
 6. The method of claim 5, wherein theinsects or acarids are selected from the Isoptera, Diptera, Blattaria(Blattodea), Hymenoptera, Siphonaptera and Acarina orders.
 7. A methodof protecting growing plants from attack or infestation by insects oracarids comprising: applying to the foliage of the plants, or to thesoil or water in which they are growing, a pesticidally effective amountof a composition or a compound of formula I:

wherein X is chloro or bromo; Y is chloro or trifluormethyl; and A and Bare hydrogen or methyl with the proviso that one of A or B must bemethyl; or the enantiomers or salts thereof; wherein said growing plantsare protected from attack or infestation by insects or acarids.
 8. Themethod of claim 7, wherein the insects or acarids are selected from theIsoptera, Diptera, Blattaria (Blattodea), Hymenoptera, Siphonaptera andAcarina orders.
 9. A method for treating, controlling, or protectinganimals against infestation or infection by parasites comprising:orally, topically or parenterally administering or applying to animals aparasiticidally effective amount of compositions or compounds of formulaI:

wherein X is chloro or bromo; Y is chloro or trifluormethyl; and A and Bare hydrogen or methyl with the proviso that one of A or B must bemethyl; or the enantiomers or veterinarily acceptable salts thereof;wherein said animals are controlled, or protected from infestation orinfection by said parasites.
 10. A process for the preparation of acomposition for treating, controlling, or protecting animals againstinfestation or infection by parasites comprising: combining aparasiticidally effective amount of compositions or compounds of formulaI:

wherein X is chloro or bromo; Y is chloro or trifluormethyl; and A and Bare hydrogen or methyl with the proviso that one of A or B must bemethyl; or the enantiomers or veterinarily acceptable salts thereof; anda veterinarily acceptable carrier.
 11. The process as claimed in claim10 wherein the parasites are selected from the Diptera, Siphonaptera,and Ixodida orders.
 12. A composition comprising: a pesticidally orparasiticidally active amount of compounds of formula I

wherein X is chloro or bromo; Y is chloro or trifluormethyl; and A and Bare hydrogen or methyl with the proviso that one of A or B must bemethyl; or the enantiomers or veterinarily acceptable salts thereof; andan agronomically or veterinarily acceptable carrier.
 13. A synergisticmixture comprising: a compound of formula I

wherein X is chloro or bromo; Y is chloro or trifluormethyl; and A and Bare hydrogen or methyl with the proviso that one of A or B must bemethyl; or the enantiomers or salts thereof; and at least one otherpesticide in synergistically effective amounts, wherein the observedmortality of the synergistic mixture of the compound of formula I andthe at least one other pesticide is greater than the expected mortalityof the compound of formula I and the at least one other pesticide.